KR20190052707A - A decorative sheet and a cosmetic material using the same - Google Patents

Abstract

The present invention provides a cosmetic sheet having excellent processing characteristics, weather resistance and durability, and a cosmetic material using the same. At least one of the substrate and the surface protective layer comprises a white pigment, the surface protective layer is a cured product of the curable resin composition, and the martens hardness is at least 9 N / mm < 2 ≪ 2 > or less and a cosmetic material using the same.

Description

A decorative sheet and a cosmetic material using the same

The present invention relates to a cosmetic sheet and a cosmetic material using the same.

Furniture, or pharmacopoeial products other than the interior or exterior members of a building such as a wall, a ceiling, a floor, and a doorway, a window or a door of a door, a railing, a lantern, In general, a metal member such as a steel plate, a resin member, or a woody member is used as an adherend and a decorative sheet is adhered to these adherends for the surface lining board of a cabinet such as an appliance or the exterior member of a vehicle. When the decorative sheet is adhered to the adherend, it is common to perform bending such as V-cutting and lapping. If the processing characteristics of the decorative sheet are poor, cracks will be introduced into the bending portion and whitening will occur Throw away.

In order to solve such a problem, there has been proposed a method for producing a transparent resin film, which comprises a base sheet, a pattern layer, a transparent resin layer and a surface protective layer, the surface protective layer is formed of a composition comprising an ionizing radiation curable resin, There has been proposed a decorative sheet in which a colored resin layer using a predetermined resin is formed in a concave portion (for example, Patent Document 1).

Patent Document 1: JP-A-2006-095992

However, in order to use the decorative sheet described in Patent Document 1 in a member used in an environment exposed to direct sunlight such as an exterior member such as a doorway door, a window frame such as a window frame, a door, or the like, The surface protection layer or the like is gradually deteriorated around the bent portion as the outdoor exposure time elapses, resulting in cracking and peeling, and the long-term weatherability is poor .

However, the decorative sheet used for members such as exterior members, window frames and the like is required to have anti-icing properties in addition to processing characteristics and weather resistance. In order to obtain excellent machining characteristics, it is necessary to use a material having flexibility. On the other hand, it is difficult to obtain excellent machinability with a material having flexibility, and machining characteristics and durability are opposite to each other.

An object of the present invention is to provide a cosmetic sheet having excellent processing characteristics, weather resistance, and durability, and a cosmetic material using the same, which has been made under such circumstances.

Means for Solving the Problems The inventor of the present invention has conducted intensive studies in order to solve the above problems and found that as a factor that causes deterioration of long-term weatherability, there is a fine crack that occurs to such an extent that it can not be visually recognized when a decorative sheet is bonded to an adherend, In addition, as long as the outdoor exposure time has elapsed, fine cracks are gradually enlarged, and weathering agents such as ultraviolet absorbers are bleed out (also referred to as " bleed out transition ") from enlarged cracks, When the layer falls off, the layer lower than the surface protective layer is exposed and exposed to direct sunlight, whereby the deterioration of each layer of the decorative sheet is progressed and the weather resistance is lowered. Particularly, when a white pigment of titanium oxide is contained in a base material and a decorative layer, when the ultraviolet rays in sunlight reach the titanium oxide in these layers, the titanium oxide is excited by ultraviolet rays to exhibit a photocatalytic effect, And the resin constituting the decorative layer or the like are degraded or deteriorated. The inventor of the present invention has found that the weather resistance can be improved by suppressing the influence of the use of a white pigment such as titanium oxide in a base material and a decorative layer. The inventor of the present invention has found that the above object can be solved by the invention relating to a cosmetic sheet having the following constitution and a cosmetic material using the same.

At least one of the substrate and the surface protective layer contains a white pigment, the surface protective layer is a cured product of the curable resin composition, and the martens hardness is at least 9 N / mm < 2 ≪ 2 > or less.

[2] The decorative sheet according to [1], wherein the decoration layer is provided between the substrate and the surface protection layer, and at least one of the base material and the decorative layer contains a white pigment.

[3] A photothermographic material comprising at least one layer of a resin layer and a primer layer between a substrate and a surface protective layer, wherein at least one of the surface protective layer and the resin layer and the primer layer contains an ultraviolet absorber. A decorative sheet according to [2].

[4] The decorative sheet according to any one of [1] to [3], wherein the surface protective layer has a concave portion on a surface opposite to the surface on the substrate side.

[5] A cosmetic material having the adhering material and the decorative sheet according to any one of [1] to [4].

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a cosmetic sheet having excellent processing characteristics, weather resistance, and durability, and a cosmetic material using the same.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic view showing a cross section of an example of a decorative sheet of the present invention. Fig.
2 is a schematic view showing a cross section of an example of the decorative sheet of the present invention.
3 is a schematic cross-sectional view showing an example of the layer structure of the cosmetic material of the present invention.

[Make-up sheet]

The decorative sheet of the present invention comprises a base material and a surface protective layer, at least one of the base material and the surface protective layer contains a white pigment, the surface protective layer is a cured product of the curable resin composition, and the Martens hardness is 9 N / Or more and 25 N / mm < 2 > or less. The construction of the decorative sheet of the present invention will be described with reference to Figs. 1 and 2. Fig. 1 is a schematic diagram showing a cross section of an example of the decorative sheet 10 of the present invention and includes a substrate 11 and a surface protective layer 16 and a white pigment 18 is contained in the substrate 11 . Fig. 2 is a schematic view showing a cross section of an example of a preferred embodiment of the decorative sheet 10 of the present invention. The decorative sheet 10 includes a substrate 11, a decorative layer 12, an adhesive layer 13, A backing primer layer 17 is provided on the surface of the substrate 11 opposite to the surface on the side of the surface protective layer 16, The base material (11) and the decorative layer (12) contain a white pigment (18). 2, the surface protective layer 16 has a concave portion 19 on the surface (the outermost surface) opposite to the substrate 11, and the concave portion 19 is provided with a surface protective layer 16 , Reaching the resin layer (14), reaching the substrate (11), and the like.

(Martens hardness)

The decorative sheet of the present invention has a Martens hardness of 9 N / mm2 or more and 25 N / mm2 or less. If the hardness of the Martens is less than 9 N / mm < 2 >, the shatter resistance can not be obtained. If the hardness is more than 25 N / mm < 2 > Specifically, the measurement of the hardness of the martens in the present invention is a value measured using a micro-hardness meter. While the load is continuously increased at room temperature (23 DEG C), a pyramidal diamond indenter is formed on the surface of the sample (Mm 2) from the diagonal length of the pyramidal recess formed on the surface, and dividing the test load F (N) when the indentation depth reaches 2 탆 by the surface area A Is a calculated value. As the micro-hardness tester, for example, a micro hardness tester " Pico Denta HM-500 " (manufactured by Fisher Instruments) may be used.

In the present invention, it is found out that there is a correlation between the magnitude of the martens hardness and the occurrence of fine cracks in the surface of the decorative sheet (surface protective layer) when the decorative sheet is bended, and the martens hardness is set within a predetermined range, By setting the Martens hardness to a predetermined upper limit or less, it is possible to suppress the generation of fine cracks in the surface protective layer in the bending process of the decorative sheet, and furthermore, the dropout of the surface protective layer over time can be suppressed. As a result, the surface protective layer is formed by continuously covering the surface of each layer positioned on the side of the adherend with respect to the surface protective layer such as the substrate, the decorative layer, the resin layer and the primer layer, Thereby preventing direct contact with the layer. In particular, in the case of containing the ultraviolet absorbent in the layer on the surface side (that is, on the sunlight incidence side) of the layer containing the white pigment made of titanium oxide, the ultraviolet absorbent in each layer from the cracks in the surface protective layer bleeds out, The photocatalytic effect of the titanium oxide pigment due to the loss of the ultraviolet absorber in the same layer accompanied with the detachment of the surface protective layer with the lapse of time is suppressed.

As a result, it has become possible to obtain excellent weatherability even under long and severe environments. Further, by setting the magnitude of the Martens hardness to within a predetermined range, and particularly to a predetermined lower limit value or more, excellent anti-image resistance can be obtained.

The Martens hardness is preferably 10 N / mm2 or more and 22 N / mm2 or less, more preferably 12 N / mm2 or more and 20 N / mm2 or less from the viewpoints of improving processing characteristics, weather resistance, and resistance. In the present specification, the numerical values according to "above", "below" and "to" regarding the description of the numerical range are numerical values which can be arbitrarily combined.

The Martens hardness can be adjusted mainly by various constitutions of the base material and the surface protective layer. For example, the Martens hardness can be adjusted to 9 N / mm < 2 > Or more and 25 N / mm < 2 > or less.

Hereinafter, each layer constituting the decorative sheet of the present invention will be described.

(materials)

The base material can be usually employed as a base material of a decorative sheet, and a resin base material made of a thermoplastic resin is typically used. Examples of the thermoplastic resin include polyolefin resins such as polypropylene and polyethylene, polyester resins, polycarbonate resins, acrylonitrile-butadiene-styrene resins (hereinafter also referred to as " ABS resins "), acrylic resins, Is used. Among them, a polyolefin resin, a polyester resin, a polycarbonate resin, a vinyl chloride resin and an ABS resin are preferable in view of processing characteristics, and a polyolefin resin is particularly preferable. In the present invention, these resins may be used singly or in combination of plural kinds thereof.

The polyolefin resin is not particularly limited and examples of the polyolefin resin include polyethylene (low density, medium density, high density), polypropylene, polymethylpentene, polybutene, ethylene-propylene copolymer, propylene-butene copolymer, ethylene- Acrylic acid copolymers, ethylene-propylene-butene copolymers, and polyolefin thermoplastic elastomers. Of these, polyethylene (low density, medium density, high density), polypropylene, ethylene-propylene copolymer and propylene-butene copolymer are preferable.

In the decorative sheet of the present invention, at least one of the base material and the surface protective layer needs to contain a white pigment. The white pigment may be contained only in the base material, or may be contained only in the surface protective layer, good. In the present invention, it is preferable that the base material is a colored resin base material containing a white pigment. By using the resin base material colored by the white pigment, it is easy to conceal the surface hue well when the surface color of the adherend to which the decorative sheet is adhered is not uniform, more excellent designability can be obtained, The color stability of the decorative layer can be improved. On the other hand, when a decorative sheet containing a white pigment is used in an environment exposed to direct sunlight, there is a fear of weatherability due to its photocatalytic function. However, in the present invention, it has become possible to reduce the influence of the white pigment on the weather resistance by using the surface protective layer as a cured product of the curable resin composition and the decorative sheet having a predetermined martens hardness.

Examples of the white pigment include titanium oxide (titanium white), lead white, antimony white, and titanium dioxide coated mica. These may be used singly or in combination. In the present invention, titanium oxide (titanium white) is preferable in view of concealability (coloring), ease of handling, and the like.

Examples of the titanium oxide include anatase-type, brookite-type, and rutile-type. Any of them can be used, but rutile type is preferable in view of excellent hiding power (color development) and weatherability. Since the rutile type titanium oxide has low photocatalytic activity, the photocatalytic reaction hardly occurs even when used in an environment exposed to direct sunlight, and the influence on the weather resistance by the photocatalytic reaction is reduced, and the weather resistance is improved.

The white pigment is preferably subjected to a surface treatment in view of selecting a low photocatalytic activity in consideration of weatherability. As the surface-treated white pigment, for example, those surface-treated with an inorganic metal hydrous oxide and coated with inorganic hydrous oxide fine particles are preferably used. Examples of the inorganic metal hydrous oxide include alumina, silica, titania, zirconia, tin oxide, antimony oxide, and zinc oxide. Further, titanium oxide whose surface is untreated or titanium oxide surface-treated with the above inorganic metal hydroxides may be surface-treated with a coupling agent such as a silane coupling agent, a titanate coupling agent or an aluminum coupling agent, or a silicone oil or a fluorine- It is also preferable to make the surface hydrophobic or lipophilic. In the present invention, the above-mentioned surface treatment may be carried out alone, or a white pigment which is a combination of a plurality of surface treatments may be used.

In the present invention, surface treatment with alumina, silica or zinc oxide is preferable from the viewpoint of obtaining excellent hiding power, surface treatment with alumina or silica is more preferable, and surface treatment with alumina and silica is particularly preferable .

The average particle diameter of the primary particles of the white pigment is preferably 0.02 to 1.5 탆, more preferably 0.15 to 0.5 탆, and even more preferably 0.1 to 0.3 탆. When the average particle diameter of the white pigment is within the above-mentioned range, excellent coloring can be obtained, and designability can be obtained with high hiding. Here, the average particle diameter is a value that can be obtained as a mass average value D50 in the particle size distribution measurement by the laser diffraction method.

When the base material is a colored resin base material containing a white pigment, the mode of coloring is not particularly limited and may be transparent coloring or opaque coloring (concealing coloring), and these may be arbitrarily selected. For example, when the background color of the adherend such as a steel sheet to which a decorative sheet is adhered is colored and concealed, opaque coloring may be selected. On the other hand, when the base shape of the adherend used in the cosmetic material can be visually confirmed, transparent coloring can be selected.

The content of the white pigment is appropriately adjusted depending on whether it is colored transparent or opaque (hiding colored). For example, it is preferably 1 part by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the resin constituting the substrate, More preferably 3 parts by mass or more and 40 parts by mass or less, still more preferably 5 parts by mass or more and 30 parts by mass or less, and particularly preferably 5 parts by mass or more and 20 parts by mass or less.

The substrate may contain a coloring agent other than the white pigment. For example, inorganic pigments such as iron black, yellow lead, titanium yellow, reddish brown, cadmium red, group blue and cobalt blue; Organic pigments or dyes such as quinacridone red, isoindolinone yellow, nickel azo complex, phthalocyanine blue and the like; Metal pigments comprising scaly flakes such as aluminum and brass; And a coloring agent such as a pearl luster pigment (pearl pigment) comprising scaly flakes such as titanium dioxide coated mica and basic carbonate liquor.

An additive may be added to the substrate, if necessary. Examples of additives include inorganic fillers such as calcium carbonate and clay, flame retardants such as magnesium hydroxide, antioxidants, lubricants, foaming agents, ultraviolet absorbers, and light stabilizers. The blending amount of the additive is not particularly limited as long as it does not hinder the processing characteristics, and can be appropriately set in accordance with the required characteristics and the like.

Among the above additives, from the viewpoint of improving the weather resistance of the decorative sheet of the present invention, it is preferable to use an antiwear agent such as an ultraviolet absorber or a light stabilizer, and it is particularly preferable to use a light stabilizer.

Since the base material is a layer positioned between the surface protective layer and the adherend when it is made of a cosmetic material, the influence on the deterioration of the weather resistance due to bleeding out of the endurance agent such as an ultraviolet absorber or a light stabilizer, It can be said that it is small. The ultraviolet absorber to be used for the substrate is not particularly limited, and examples thereof include a benzotriazole-based ultraviolet absorber, a benzophenone-based ultraviolet absorber, and a triazine-based ultraviolet absorber. Further, the specific hydroxyphenyl triazine-based ultraviolet absorber exemplified as being particularly preferably used in a surface resin layer described later can be preferably used, of course.

As the light stabilizer, hindered amine light stabilizers are preferable, and examples thereof include 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, 1,2,2,6,6-pentamethyl- (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) Sebacate, bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidinyl ), Sebacate, methyl (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, 2,4-bis [N-butyl- Tetramethyl-4-piperidinyl) amino] -6- (2-hydroxyethylamine) -1,3,5-triazine), tetrakis (1,2,2,6,6- Pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, bis- (1,2,2,6,6-pentamethyl-4-piperidyl) -2 - (3,5-di-t-butyl-4-hydroxy-benzyl) -2-n-butylmalonate. Of these, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis Tetramethyl-4-piperidinyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, methyl (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate, and the like, which are derived from decane diacid (sebacic acid).

These ultraviolet absorbers and light stabilizers may be used singly or in combination of plural kinds thereof. The ultraviolet absorber and light stabilizer may be one having a reactive functional group having an ethylenic double bond such as a (meth) acryloyl group, a vinyl group or an allyl group as exemplified above as one of the light stabilizers.

The content of the ultraviolet absorber in the substrate is preferably not less than 0.1 parts by mass and not more than 5 parts by mass, more preferably not less than 0.2 parts by mass and not more than 3 parts by mass based on 100 parts by mass of the resin constituting the substrate, more preferably not less than 0.3 parts by mass and not less than 2 parts by mass Or less. The content of the light stabilizer in the base material is preferably 0.5 parts by mass or more and 10 parts by mass or less, more preferably 1 part by mass or more and 8 parts by mass or less, and still more preferably 3 parts by mass or more More preferably 6 parts by mass or less. When the content of the ultraviolet absorber and the light stabilizer in the substrate is within the above range, an excellent addition effect can be obtained without bleeding out.

The substrate may be a monolayer of the resin, or a multilayer of a homogeneous or heterogeneous resin.

The thickness of the base material is preferably from 20 to 150 μm, more preferably from 25 to 120 μm, further preferably from 30 to 100 μm, particularly preferably from 40 to 80 μm, Or less.

The substrate may be subjected to a surface treatment such as a physical surface treatment such as an oxidation method or an irregularization method or a chemical surface treatment or the like on the one surface or both surfaces thereof in order to improve the interlayer adhesion between the substrate and another layer, Can be performed.

Examples of the oxidation method include a corona discharge treatment, a chromium oxidation treatment, a flame treatment, a hot air treatment, and an ozone-ultraviolet treatment. Examples of the irregularity include a sandblast method and a solvent treatment method. These surface treatments are appropriately selected in accordance with the kind of the substrate. In general, the corona discharge treatment method is preferably used in terms of surface treatment effect and operability.

In order to improve the interlayer adhesion between the substrate and other layers, to enhance the adhesion with various adherends, and further to suppress the deterioration by the white pigment, a treatment such as forming a primer layer and a back primer layer on the substrate . These primer layers will be described later.

(Surface protective layer)

The surface protective layer is a cured product of the curable resin composition, and it is a cured product of the curable resin composition, and it is possible to improve the interlayer adhesion of the decorative layer, the substrate or the decorative layer and the surface protective layer, Which is located on the outermost surface of the decorative sheet of the present invention, formed on the primer layer in order to reduce the influence on the deterioration of the surface protective layer by the above- By having such a surface protective layer, the decorative sheet of the present invention has superior machining characteristics and also has resistance to weather and weather.

The surface protective layer is composed of a cured product of a curable resin composition containing a curable resin.

As the curable resin used for forming the surface protective layer, a thermosetting resin such as a two-liquid curable resin, an ionizing radiation curable resin and the like are preferably used, and an ionizing radiation curable resin and a thermosetting resin Or a so-called hybrid type in which a curable resin and a thermoplastic resin are used in combination.

The curable resin is preferably an ionizing radiation curable resin from the viewpoint of increasing the crosslinking density of the resin constituting the surface protective layer to improve the resistance to weathering and weatherability and also from the viewpoint that the resin can be applied without solvent and is easy to handle , And an electron beam-curable resin is more preferable.

(Ionizing radiation curable resin)

The ionizing radiation curable resin means a resin which is crosslinked and cured by irradiation with ionizing radiation and has an ionizing radiation curable functional group. Here, the ionizing radiation curable functional group is a group capable of crosslinking and curing upon irradiation with ionizing radiation, and is preferably a functional group having an ethylenic double bond such as a (meth) acryloyl group, a vinyl group or an allyl group. The term "ionizing radiation" used herein means having both of energy capable of polymerizing or crosslinking a molecule in an electromagnetic wave or a charged particle beam. Usually, ultraviolet rays (UV) or electron beams (EB) And charged particle lines such as electromagnetic waves, alpha rays, and ion beams.

As the ionizing radiation curable resin, specifically, a polymerizable monomer and a polymerizable oligomer conventionally used as an ionizing radiation curable resin can be appropriately selected and used.

As the polymerizable monomer, a (meth) acrylate-based monomer having a radically polymerizable unsaturated group in the molecule is preferable, and a polyfunctional (meth) acrylate monomer is particularly preferable. Here, "(meth) acrylate" means "acrylate or methacrylate".

Examples of the polyfunctional (meth) acrylate monomer include (meth) acrylate monomers having two or more ionizing radiation-curable functional groups in the molecule and having at least a (meth) acryloyl group as the functional group.

The number of functional groups is preferably 2 or more and 8 or less, more preferably 2 or more and 6 or less, still more preferably 2 or more and 4 or less, particularly preferably 2 or more and 3 or less from the viewpoints of improving processing characteristics, weather resistance and weather resistance Do. Examples of the (meth) acrylate monomer having two or more radical polymerizable unsaturated groups in these molecules include diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 1,6-hexanediol di (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tripentaerythritol Octaacrylate and the like. These multifunctional (meth) acrylates may be used singly or in combination of plural kinds thereof.

Examples of the polymerizable oligomer include (meth) acrylate oligomers having two or more ionizing radiation-curable functional groups in the molecule and having at least a (meth) acryloyl group as the functional group. (Meth) acrylate oligomer, a polycarbonate (meth) acrylate oligomer, an acrylic (meth) acrylate oligomer, a polyester (meth) acrylate oligomer, Late oligomers and the like.

Examples of the polymerizable oligomer include polybutadiene (meth) acrylate oligomer having high hydrophobicity having a (meth) acrylate group in the side chain of the polybutadiene oligomer, silicone (meth) acrylate oligomer having polysiloxane bond in the main chain, An aminoplast resin (meth) acrylate oligomer modified with an aminoplast resin having a large number of reactive groups in a small molecule, a cationic oligomer having a cation in a molecule such as a novolak type epoxy resin, a bisphenol type epoxy resin, an aliphatic vinyl ether or an aromatic vinyl ether Oligomers having polymerizable functional groups, and the like.

These polymerizable oligomers may be used singly or in combination of plural kinds thereof. (Meth) acrylate oligomer, polyester (meth) acrylate oligomer, polyether (meth) acrylate oligomer, polycarbonate (meth) acrylate oligomer, (Meth) acrylate oligomer and acrylic (meth) acrylate oligomer are preferable, and urethane (meth) acrylate oligomer and polycarbonate (meth) acrylate oligomer are more preferable, and urethane (meth) acrylate oligomer is more preferable.

The number of functional groups of these polymerizable oligomers is preferably 2 to 8, more preferably 6 or less, still more preferably 4 or less, and most preferably 3 or less, from the viewpoint of improving processing characteristics, .

The weight average molecular weight of these polymerizable oligomers is preferably from 2,500 to 7,500, more preferably from 3,000 to 7,000, and still more preferably from 3,500 to 6,000 from the viewpoint of improving processing characteristics, resistance to chemicals and weather resistance . Here, the weight average molecular weight is an average molecular weight measured by GPC analysis and converted into standard polystyrene.

In the present invention, a monofunctional (meth) acrylate may suitably be used in combination with the multifunctional (meth) acrylate or the like within the range not impairing the object of the present invention, for the purpose of lowering the viscosity thereof . These monofunctional (meth) acrylates may be used singly or in combination of plural kinds.

In the present invention, as the ionizing radiation curable resin, it is preferable to include a polymerizable oligomer from the viewpoint of improving processing characteristics, resistance to weathering and weatherability. The content of the polymerizable oligomer in the ionizing radiation curable resin is preferably 80% by mass or more, more preferably 90% by mass or more, still more preferably 95% by mass or more, and particularly preferably 100% by mass.

The surface protective layer may contain a white pigment. As the white pigment, those exemplified as white pigments contained in the base material can be used. When the white pigment is contained in the surface protective layer, the content of the white pigment is preferably 1 part by mass or more and 30 parts by mass or less, more preferably 3 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the resin constituting the surface protective layer More preferably 5 parts by mass or more and 10 parts by mass or less.

The surface protective layer may contain additives such as an ultraviolet absorber, an ultraviolet shielding agent, a light stabilizer, a wear resistance improver, a polymerization inhibitor, a crosslinking agent, an infrared absorbent, an antistatic agent, an adhesion improver, a leveling agent, A tackifier, a coupling agent, a plasticizer, a defoaming agent, a filler, an antiblocking agent, a lubricant, and a solvent.

From the viewpoint of improving the weather resistance of the decorative sheet of the present invention, it is preferable to use a surface protecting layer such as an ultraviolet absorber or a light stabilizer among the above additives. As for the light stabilizer, in view of this, at least one of the substrate and the surface protective layer preferably contains a light stabilizer, and more preferably, the substrate and the surface protective layer include a light stabilizer.

 Examples of the ultraviolet absorber include benzotriazole-based ultraviolet absorbers, benzophenone-based ultraviolet absorbers, triazine-based ultraviolet absorbers and the like exemplified as ultraviolet absorbers that can be contained in the substrate, and triazine-based ultraviolet absorbers are preferable. Among the triazine-based ultraviolet absorbers, a hydroxyphenyltriazine-based ultraviolet absorber in which at least one organic group selected from organic groups including a hydroxyphenyl group, an alkoxyphenyl group and those groups is connected to a triazine ring is more preferable, And a hydroxyphenyltriazine based ultraviolet absorber represented by the general formula (1) is more preferable. Since the surface protective layer is a layer positioned on the outermost surface of the decorative sheet, it is preferable that it is difficult to bleed out from the layer. The hydroxyphenyltriazine type ultraviolet absorbent represented by the following general formula (1) , It is expected to be difficult to bleed out, and it is particularly preferable as an ultraviolet absorbent for use in the surface protective layer from the viewpoint of weatherability.

In the general formula (1), R ¹¹ is a divalent organic group, R ¹² is an ester group represented by -C (= O) OR ¹⁵ , R ¹³ , R ¹⁴ and R ¹⁵ each independently represent a monovalent organic group , And n ₁₁ and n ₁₂ are each independently an integer of 1 to 5.

Examples of the divalent organic group represented by R ¹¹ include aliphatic hydrocarbon groups such as an alkylene group and an alkenylene group. From the viewpoint of weather resistance, an alkylene group is preferable, and the number of carbon atoms thereof is preferably 1 or more and 20 or less, More preferably 1 or more and 8 or less, still more preferably 1 or more and 4 or less. The alkylene group and alkenylene group may be any of linear, branched, and cyclic, but linear and branched are preferable.

Examples of the alkylene group having 1 to 20 carbon atoms include methylene, 1,1-ethylene, 1,2-ethylene, 1,3-propylene, 1,2-propylene, 2,2- (Hereinafter referred to as " various " means a straight chain, branched, or an isomer thereof), various butylene groups, various pentylene groups, various hexylene groups, various heptylene groups, various octylene groups, Various dodecylene groups, various dodecylene groups, various tridecylene groups, various tetradecylene groups, various pentadecylene groups, various hexadecylene groups, various heptadecylene groups, various octadecylene groups , Various nonadecylene groups, and various eicosylene groups.

Examples of the monovalent organic group represented by R ¹³ and R ¹⁴ include an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, and an arylalkyl group. An aromatic hydrocarbon group such as an aryl group or an arylalkyl group is preferable. Among them, a phenyl group is preferable as a monovalent organic group of R ¹³ and R ¹⁴ .

The aryl group is preferably an aryl group having 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms, and still more preferably 6 to 10 carbon atoms such as a phenyl group, various methylphenyl groups, various ethylphenyl groups, various dimethylphenyl groups , Various propylphenyl groups, various trimethylphenyl groups, various butylphenyl groups, and various naphthyl groups. The arylalkyl group is preferably an arylalkyl group having 7 to 20 carbon atoms, more preferably 7 to 12 carbon atoms, and still more preferably 7 to 10 carbon atoms, such as a benzyl group, a phenethyl group, various phenylpropyl groups, various phenyl Butyl group, various methylbenzyl groups, various ethylbenzyl groups, various propylbenzyl groups, various butylbenzyl groups, and various hexylbenzyl groups.

Examples of the monovalent organic group represented by R ¹⁵ include an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group and an arylalkyl group, and aliphatic hydrocarbon groups such as an alkyl group and an alkenyl group are preferable, and an alkyl group is more preferable. That is, as R ¹² , an alkyl ester group and an alkenyl ester group are preferable, and an alkyl ester group is more preferable.

The alkyl group is preferably an alkyl group having 1 to 20 carbon atoms, more preferably 2 to 16, and still more preferably 6 to 12, such as a methyl group, an ethyl group, various propyl groups, various butyl groups, various pentyl groups, Various octadecyl groups, various tridecyl groups, various tetradecyl groups, various pentadecyl groups, various hexadecyl groups, various heptadecyl groups, various octadecyl groups, various hexadecyl groups, various octadecyl groups, Decyl groups, various nonadecyl groups, and various eicosyl groups.

The alkenyl group is preferably an alkenyl group having 2 to 20 carbon atoms, more preferably 3 to 16 carbon atoms, and still more preferably 6 to 12 carbon atoms such as a vinyl group, various propenyl groups, various butenyl groups, various pentenyl groups, Various hexenyl groups, various octenyl groups, various nonenyl groups, various decenyl groups, various undecenyl groups, various dodecenyl groups, various tridecenyl groups, various tetradecenyl groups, various pentadecenyl groups, various hexadecenyl Group, various heptadecenyl groups, various octadecenyl groups, various nonadecenyl groups, and various econenyl groups.

As the hydroxyphenyltriazine compound represented by the general formula (1), more specifically, R ¹¹ is an alkylene group having 1 to 20 carbon atoms and R ¹² and R ¹⁵ are alkyl esters having 1 to 20 carbon atoms , R ¹³ and R ¹⁴ are aryl groups having 6 to 20 carbon atoms and n ₁₁ and n ₁₂ are 1, and R ¹¹ is an alkylene group having 1 to 12 carbon atoms, R ¹² and R ¹⁵ are alkyl ester groups having 2 to 16 carbon atoms and R ¹³ and R ¹⁴ are aryl groups having 6 to 12 carbon atoms and n ₁₁ and n ₁₂ are 1, more preferably, R ¹¹ is C 1 is more than the alkylene group of less than 8, R ¹² and R ¹⁵ is C 6 and 12 groups of the alkyl ester groups or less, R ¹³ and R ¹⁴ is C 6 or higher than 10 of the aryl group and, n ₁₁ and n ₁₂ is 1, hydroxyphenyl-triazine The compounds are more preferably, R ¹¹ is an alkyl group of more than a carbon number of 1 or 4, the R ¹² and R ¹⁵ is an ester group, an alkyl group having a carbon number of 8, R ¹³ and and R ¹⁴ is a phenyl group, n ₁₁ and n ₁₂ is 1, A hydroxyphenyltriazine compound is particularly preferable.

Specific examples of the hydroxyphenyltriazine compound represented by the general formula (1) include an ester group represented by the following formula (2) wherein R ¹¹ is an ethylene group, R ¹² and R ¹⁵ are an iso-octyl group, R ¹³ and R ¹⁴ are phenyl groups and n ₁₁ and n ₁₂ are 1, that is, 2- (2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -Bis (4-phenylphenyl) -1,3,5-triazine is preferable, and this hydroxyphenyltriazine compound is available, for example, as a commercially available product ("TINUVIN 479", manufactured by BASF).

As the light stabilizer, a hindered amine light stabilizer is preferable, and a hindered amine light stabilizer exemplified as a light stabilizer that can be used for a substrate can be used. From the viewpoint of weather resistance, a hindered amine light stabilizer such as hindered amine derived from decane diacid A dodoamine-based light stabilizer is preferable.

These ultraviolet absorbers and light stabilizers may be used singly or in combination of plural kinds thereof. The ultraviolet absorber and light stabilizer may have a reactive functional group having an ethylenic double bond such as (meth) acryloyl group, vinyl group or allyl group.

The content of the ultraviolet absorber in the surface protective layer is preferably not less than 0.1 parts by mass and not more than 10 parts by mass, more preferably not less than 0.2 parts by mass nor more than 5 parts by mass, and most preferably not more than 0.3 parts by mass based on 100 parts by mass of the resin constituting the surface protective layer More preferably not less than 3 parts by mass, and particularly preferably not less than 0.5 parts by mass but not more than 2 parts by mass.

The content of the light stabilizer in the surface protective layer is preferably 0.1 parts by mass or more and 10 parts by mass or less, more preferably 0.5 parts by mass or more and 8 parts by mass or less, based on 100 parts by mass of the resin constituting the surface protective layer, More preferably 1 part by mass or more and 5 parts by mass or less, and particularly preferably 1.5 parts by mass or more and 3 parts by mass or less. When the content of the ultraviolet absorber and the light stabilizer in the surface protective layer is within the above range, an excellent addition effect can be obtained without bleeding out.

The thickness of the surface protective layer is preferably 1.5 mu m or more and 20 mu m or less, more preferably 2 mu m or more and 15 mu m or less, further preferably 3 mu m or more and 10 mu m or less from the viewpoint of improving processing characteristics, Do.

(Decorative layer)

The decorative sheet of the present invention preferably has a decorative layer between the substrate and the surface protection layer from the viewpoint of improving the decorative property. The decorative layer may be, for example, a colored layer covering the entire surface (so-called front colored layer), a pattern layer formed by printing various shapes using an ink and a printing machine, or a combination thereof. For example, in the case of hiding the background color of the adherend, the front colored layer and the pattern layer may be combined from the viewpoint of enhancing the designability while hiding the color by forming the front colored layer and further improving the designability, . In the case of using the base material of the adhering material, only the pattern layer may be formed without forming the front colored layer.

As the ink used for the decorative layer, an appropriate mixture of a coloring agent such as a pigment and a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent, an ultraviolet absorber and a light stabilizer may be used.

The binder is not particularly limited and examples thereof include urethane resins, acrylic polyol resins, acrylic resins, ester resins, amide resins, butyral resins, styrene resins, urethane-acrylic copolymers, polycarbonate urethane-acrylic copolymers (Urethane-acrylic copolymer derived from a polymer (polycarbonate polyol) having at least two hydroxyl groups at the terminal and side chains), a vinyl chloride-vinyl acetate copolymer resin, a vinyl chloride-vinyl acetate-acrylic copolymer resin, a chlorinated Propylene resin, nitrocellulose resin, and cellulose acetate resin. These resins may be used singly or in combination. In addition to the one-liquid curing type, it is also possible to use isocyanates such as tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPID) and xylylene diisocyanate And a two-liquid curing type which is accompanied by a curing agent such as a compound.

As the colorant, a white pigment exemplified as a colorant used in the above-described base material is preferably used from the viewpoint of hiding the base color of the adhered material and hiding it and improving designability. The content of the white pigment in the decorative layer is preferably 5 parts by mass or more and 90 parts by mass or less, more preferably 15 parts by mass or more and 80 parts by mass or less, and even more preferably 30 parts by mass or more More preferably 70 parts by mass or less.

In addition, like the substrate, an inorganic pigment other than a white pigment such as iron black, chrome yellow, titanium sulfur, lesion, cadmium red, ultramarine blue, and cobalt blue; Organic pigments or dyes such as quinacridone red, isoindolinone yellow, nickel azo complex, phthalocyanine blue and the like; Metal pigments comprising flaky flakes such as aluminum and chilly oil; (Pearl) pigment made of scaly flakes such as titanium dioxide-coated mica, basic carbonate flakes and the like may be used.

From the viewpoint of improving the weather resistance, the decorative layer preferably contains a heat-resistant agent such as an ultraviolet absorber and a light stabilizer, and more preferably includes a light stabilizer.

Examples of ultraviolet absorbers and light stabilizers include ultraviolet absorbers and light stabilizers exemplified as being included in the substrate and the surface protective layer. The content of the ultraviolet absorber may be the same as the content in the surface protective layer from the viewpoint of improvement in weather resistance. The content of the light stabilizer is preferably 0.1 parts by mass or more and 10 parts by mass or less, more preferably 0.2 parts by mass or more and 5 parts by mass or less, and still more preferably 0.3 parts by mass or more and 3 parts by mass or less with respect to 100 parts by mass of the resin constituting the substrate More preferably 0.5 part by mass or more and 2 parts by mass or less.

 In the case of having a pattern layer as a decorative layer, it may be in the shape of a lozenge, a marble pattern (e.g., travertine marble pattern) or the like, Tile attaching shape, brick pile shape, etc., and a combination of them, patchwork, etc. There are also shapes. These shapes are formed not only by multicolor printing by the usual process colors of yellow, red, blue, and black, but also by multi-color printing by the characteristic color of preparing individual color plates constituting the shape.

The thickness of the decorative layer may be appropriately selected according to the desired pattern. However, from the viewpoint of coloring concealment of the background color of the adherend and improvement of designability, it is preferably 0.5 탆 or more and 20 탆 or less, more preferably 1 탆 or more and 10 탆 or less And more preferably 2 mu m or more and 5 mu m or less.

(Resin layer)

The resin layer is a layer which is preferably formed as desired in view of protection of the decorative layer, processing characteristics, and resistance to weathering and weathering.

As the resin constituting the resin layer, for example, a polyolefin resin, a polyester resin, an acrylic resin, a polycarbonate resin, a polyurethane resin, a polystyrene resin, a vinyl chloride resin and a vinyl acetate resin are preferably used. Among them, a polyolefin resin and a polyester resin are preferable, and a polyolefin resin is more preferable from the viewpoints of processing characteristics, resistance to wear and weatherability. As the polyolefin resin, a resin exemplified as one capable of constituting the substrate can be enumerated, and among them, a polypropylene resin is preferable.

It is preferable that the resin layer be formed between the substrate sheet and the surface protection layer. In the case where the resin layer has a decorative layer, it is preferable that the resin layer is disposed between the decorative layer and the surface protection layer from the viewpoint of protecting the decorative layer.

The resin layer may be transparent or opaque. When the resin layer is formed between the decorative layer and the surface protection layer, it is preferable that the resin layer is transparent in view of enabling the decorative layer to be visually recognized more clearly. Here, transparency includes not only colorless transparency but also colored transparency and translucency. Further, when colored, the colorant to be used is preferably the same as the colorant used in the above-mentioned base material, and a white pigment can be preferably used.

The resin layer may be blended with an additive agent as needed, and examples of the additive agent that can be incorporated in the above-described base material may be used. From the viewpoint of improving the weather resistance of the decorative sheet of the present invention, among these additives, it is preferable to use a heat-resistant agent such as an ultraviolet absorber or a light stabilizer, and it is particularly preferable to use a light stabilizer.

Examples of the ultraviolet absorber and the light stabilizer include ultraviolet absorbers and light stabilizers exemplified as those usable for the substrate and the surface protective layer. The content of the ultraviolet absorber in the resin layer is preferably 0.1 parts by mass or more and 15 parts by mass or less, more preferably 0.2 parts by mass or more and 10 parts by mass or less, based on 100 parts by mass of the resin constituting the resin layer from the viewpoint of improvement in weather resistance More preferably 0.3 parts by mass or more and 5 parts by mass or less. The content of the light stabilizer may be the same as the content of the light stabilizer in terms of improving the weather resistance.

The thickness of the resin layer is preferably 10 탆 or more and 150 탆 or less, more preferably 30 탆 or more and 120 탆 or less, and more preferably 50 탆 or more and 100 탆 or less from the viewpoints of protection of the decorative layer, Or less.

In addition, from the viewpoint of protecting the ornamental layer and obtaining excellent durability, it is preferable to make it thicker than the substrate sheet.

The resin layer can be subjected to a surface treatment such as a physical surface treatment such as an oxidation method, an unevenness method, or a chemical surface treatment on one side or both sides thereof in order to improve interlaminar adhesion between the resin layer and another layer. These physical or chemical surface treatments are preferably exemplified by the same method as the surface treatment of the substrate described above.

Further, a treatment such as forming a primer layer on one side or both sides of the resin layer may be carried out in order to improve the interlayer adhesion between the resin layer and the other layer, and to obtain the effect of suppressing the influence of the white pigment . The primer layer will be described later.

(Primer layer)

In the decorative sheet of the present invention, the primer layer can be disposed according to the desire. The primer layer differs from the primer layer in the required effect depending on the region where it is formed, and is mainly arranged to obtain an effect of improving the interlayer adhesion and suppressing the influence of the white pigment.

For example, when it is formed between a substrate and a surface protective layer, excellent weather resistance of the surface protective layer can be obtained owing to the effect of improving the interlayer adhesion between the substrate and the surface protective layer and the effect of suppressing the influence of the white pigment contained in the substrate, When the resin layer is formed between the resin layer and the surface protective layer, the effect of improving the adhesion between the resin layer and the surface protective layer and the effect of suppressing the influence of the white pigment contained in the substrate and the decorative layer When the decorative layer and the resin layer are formed and formed between the decorative layer and the resin layer, the effect of improving the interlayer adhesion between the decorative layer and the resin layer and the effect of suppressing the influence of the white pigment contained in the decorative layer Excellent weather resistance is obtained by the effect. Further, in the case where the primer layer is formed on the surface opposite to the surface protective layer side of the substrate (the primer layer in this case is also referred to as the " back primer layer "), the interlayer adhesion between the substrate and the adherend is improved, It is possible to obtain an effect of suppressing the influence of the white pigment contained in the white pigment on the adherend.

In the decorative sheet of the present invention, the primer layer is formed between the substrate and the surface protective layer, or between the resin layer and the surface protective layer when the resin layer is provided, and on the surface opposite to the surface protective layer side of the substrate desirable.

For the formation of the primer layer, a resin composition in which a binder, a stabilizer, a plasticizer, a catalyst, a curing agent, an ultraviolet absorber, a light stabilizer, and the like are appropriately mixed with the binder is used. Examples of the binder include those exemplified as binders usable in the above decorative layer, that is, examples of the binder include urethane resin, acrylic polyol resin, acrylic resin, ester resin, amide resin, butyral resin, styrene resin, urethane- (A urethane-acrylic copolymer derived from a polymer (polycarbonate polyol) having a polymeric backbone with a carbonate bond and having a terminal and two or more hydroxyl groups in the side chain), a vinyl chloride-vinyl acetate copolymer resin, a vinyl chloride- A vinyl chloride-vinyl acetate-acrylate copolymer resin, a chlorinated propylene resin, a nitrocellulose resin (super screen), and a cellulose acetate resin. For example, a mixture of a polycarbonate-based urethane-acrylic copolymer and an acrylic polyol resin can be used as a binder.

In addition to the one-liquid curing type, it is also possible to use isocyanates such as tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPID) and xylylene diisocyanate And a two-liquid curing type which is accompanied by a curing agent such as a compound.

From the viewpoint of improving the weather resistance, it is preferable that the primer layer contains an antiwear agent such as an ultraviolet absorber or a light stabilizer. Examples of ultraviolet absorbers and light stabilizers include ultraviolet absorbers and light stabilizers which are exemplified as being included in the substrate and the surface protective layer.

The content of the ultraviolet absorber in the primer layer is preferably 1 part by mass or more and 40 parts by mass or less, more preferably 5 parts by mass or more and 35 parts by mass or less, and still more preferably 10 parts by mass or more, per 100 parts by mass of the resin constituting the primer layer More preferably 30 parts by mass or less, and particularly preferably 15 parts by mass or more and 25 parts by mass or less.

The content of the light stabilizer in the primer layer is preferably 0.5 parts by mass or more and 20 parts by mass or less, more preferably 1 part by mass or more and 15 parts by mass or less, and even more preferably 1.5 parts by mass or less with respect to 100 parts by mass of the resin constituting the primer layer More preferably not less than 10 parts by mass, and particularly preferably not less than 2 parts by mass and not more than 8 parts by mass. When the content of the ultraviolet absorber and the light stabilizer in the primer layer is within the above range, an excellent addition effect can be obtained.

The thickness of the primer layer is preferably 1 mu m or more and 10 mu m or less, more preferably 2 mu m or more and 8 mu m or less, and more preferably 3 mu m or more and 6 mu m or less from the viewpoint of improving interlayer adhesion and suppressing the influence of white pigment Is more preferable.

(Content of ultraviolet absorber)

In the case where the decorative layer of the present invention has at least one layer of a resin layer and a primer layer between the substrate and the surface protective layer, the surface protective layer, the resin layer and the primer layer It is preferable that at least one layer of the layer contains an ultraviolet absorber.

In this case, it is preferable that the content (M ₁ ) of the ultraviolet absorber in at least one of the resin layer and the primer layer is larger than the content (M ₂ ) of the ultraviolet absorber in the surface protective layer, that is, .

Content (M ₁ )> Content (M ₂ )

The content of the ultraviolet absorber in the at least one layer of the resin layer and the primer layer and the content of the ultraviolet absorber in the surface protective layer are set to be in the above-described relationship, it becomes possible to further suppress the deterioration of the weather resistance due to bleeding out of the ultraviolet absorber, Can be improved. The ultraviolet absorber contained in the resin layer and the primer layer sandwiched between the substrate and the surface protective layer and the ultraviolet absorber in the resin layer and the primer layer as well as the surface protective layer, The bleeding-out of the decorative sheet can be suppressed, and the content of the ultraviolet absorber retained in the decorative sheet can be maintained even by long-term use, whereby excellent weather resistance can be obtained.

Here, the "content of the ultraviolet absorber in the layer" means the "content of the ultraviolet absorber in 100 parts by mass of the resin forming the layer". Further, "the content (M ₁ ) of the ultraviolet absorber in at least one of the resin layer and the primer layer is larger than the content (M ₂ ) of the ultraviolet absorber in the surface protective layer" means that (i) (M ₂ ) of the ultraviolet absorber in the resin layer or the primer layer is larger than the content (M ₂ ) of the ultraviolet absorber in the surface protective layer, and (ii) When one of the resin layer and the primer layer contains an ultraviolet absorber, it is preferable that the content (M ₁ ) of the ultraviolet absorber contained in any one layer, as in the case of (i) a case means that many more content (M ₂₎ of the ultraviolet absorber in the surface protective layer, and, (iii) a decorative sheet having a resin layer and the primer layer, the resin layer and the primer layer comprising a UV absorber , The content of the ultraviolet absorber in the at least one layer among the resin layer and the primer layer in the layer having the largest amount of the ultraviolet absorber is defined as "content (M ₁ )" and the content (M ₁ ) (M ₂ ) of the ultraviolet absorber.

In the case of (iii), when the resin layer and the decorative layer are provided, the primer layer is formed at two or more places, such as between the resin layer and the decorative layer, between the resin layer and the surface protective layer, There may be two or more layers. (Iii) includes the case where two or more primer layers are present. For example, when the ultraviolet absorber is contained only in the two primer layers, and when the ultraviolet absorber is included in each of the primer layer and the resin layer , All the primer layers and the case where the ultraviolet absorber is contained in the resin layer, and the like. The relationship between the content (M ₁ ) and the content (M ₂ ) is related to the resin layer and the primer layer existing between the substrate and the surface protective layer, and the relationship between the content The content of the ultraviolet absorber in the back primer layer formed on the substrate is not considered as the content (M ₁ ).

In the case of (iii) above, the content of the ultraviolet absorber in one of the resin layer and the primer layer may be larger than the content of the ultraviolet absorber in the surface protective layer, and the content of the ultraviolet absorber in the layers of both the resin layer and the primer layer Is preferably larger than the content of the ultraviolet absorber in the layer. Further, regarding the resin layer and the primer layer, the content (M ₁₁ ) of the ultraviolet absorber in the layer (primer layer) closest to the substrate becomes larger than the content (M ₁₂ ) of the ultraviolet absorber in the resin layer, The content (M ₁₁ ) of the ultraviolet absorber in the primer layer located on the side closest to the surface protective layer decreases sequentially in the layers toward the layer side and the content (M ₂ ) of the surface protective layer , That is, a relation represented by the following inequality.

Content (M ₁₁ )> Content (M ₁₂ )> Content (M ₂ )

(M ₁ + M ₂ ) of the content (M ₁ ) of the ultraviolet absorber in the at least one layer of the resin layer and the primer layer and the content (M ₂ ) of the ultraviolet absorber in the surface protective layer is preferably not less than 0.5 part by mass More preferably 1 part by mass or more, further preferably 5 parts by mass or more, and particularly preferably 10 parts by mass or more. The upper limit is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, and further preferably 25 parts by mass or less. Here, when the resin layer and the primer layer contain an ultraviolet absorber, the content (M ₁ ) is determined according to (i) to (iii) above. When the total (M ₁ + M ₂ ) is within the above range, excellent weather resistance can be obtained without inhibiting the function of each layer of the resin layer, the primer layer and the surface protective layer.

The ratio (M ₁ / M ₂ ) of the content (M ₁ ) of the ultraviolet absorber to the content (M ₂ ) of the ultraviolet absorber in the surface protective layer in at least one of the resin layer and the primer layer is preferably 1.1 or more , More preferably 3 or more, still more preferably 5 or more, and particularly preferably 10 or more. The upper limit is preferably 35 or less, more preferably 30 or less, still more preferably 25 or less, and particularly preferably 20 or less. When the ratio (M ₁ / M ₂ ) is within the above range, excellent processing characteristics, weather resistance, and resistance can be obtained. Here, when the resin layer and the primer layer contain an ultraviolet absorber, the content (M ₁ ) is determined according to (i) to (iii) above.

(Adhesive layer)

The decorative sheet of the present invention may have an adhesive layer as required. In particular, when the decorative sheet of the present invention has a resin layer, it is effective to dispose an adhesive layer when improving the interlayer adhesion between the resin layer and the decorative layer. As the adhesive constituting the adhesive layer, an adhesive commonly used in a decorative sheet can be used without limitation.

Examples of the adhesive include a urethane-based adhesive, an acrylic adhesive, an epoxy-based adhesive, a rubber-based adhesive, and the like. Among them, a urethane adhesive is preferable from the viewpoint of adhesive strength. Examples of the urethane-based adhesive include adhesives using two-component curing type urethane resins including various polyol compounds such as polyether polyol, polyester polyol and acryl polyol and a curing agent such as various isocyanate compounds described above. In addition, acrylic-polyester-vinyl acetate resin and the like are also suitable adhesives that exhibit adhesiveness easily by heating and can maintain the adhesive strength even in use at a high temperature.

The thickness of the adhesive layer is preferably from 0.1 m to 30 m, more preferably from 1 m to 15 m, and further preferably from 2 m to 10 m from the viewpoint of obtaining sufficient adhesiveness.

(Concave portion)

The decorative sheet of the present invention preferably has a concave portion on a surface (also referred to as " surface on the surface side ") opposite to the surface of the surface protective layer on the substrate side. The decorative sheet of the present invention has a concave portion, whereby a high-quality feeling due to an improvement in texture (touch) can be obtained, and designability is improved.

As shown in Fig. 2, the concave portion may be present on the surface opposite to the substrate side of the surface protective layer, and the depth of the concave portion may be within the surface protective layer or may extend to the substrate. From the viewpoint of obtaining excellent texture (touch), it is preferable not only to stay in the surface protective layer but also to reach to the resin layer, reach to the decorative layer, and to reach the substrate.

It is preferable that the maximum depth D of the concave portion and the total thickness T of the decorative sheet have a relationship of 0.15 x T? D? T from the viewpoint of improving the designability. Namely, the depth D of the concave portion and the total thickness T (D / T) is preferably 0.15 or more and 1 or less. From this point of view, the relationship between the depth D of the concave portion and the total thickness T of the decorative sheet is more preferably 0.2 x T? D? 0.9 x T and more preferably 0.25 x T? D? 0.8 x T . That is, the ratio (D / T) of the depth D of the concave portion to the total thickness T of the decorative sheet is preferably 0.2 or more and 0.9 or less, and more preferably 0.25 or more and 0.8 or less.

Further, the maximum depth of the concave portion may be relatively varied depending on the total thickness T of the decorative sheet. The more specific depth is preferably 10 mu m or more and 120 mu m or less, more preferably 20 mu m or more and 110 mu m or less, And more preferably 100 μm or less. By having such a maximum depth, the decorative sheet is not broken at the time of processing the concave portion, for example, the embossing process, and the concave portion is not finished as if it is crushed, And the designability is improved.

Here, the measurement of the maximum depth D of the concave portion was made by measuring the height from the lowest point of the concave portion to the surface of the surface protective layer with respect to arbitrary 30 concave shapes using a surface roughness shape measuring instrument with a cutoff value of 2.50 mm, Type of cutoff filter: 2RC, inclination correction method: Measured under the measurement conditions of a straight line, and the deepest one was set as the maximum depth.

Examples of the shape of the concave portion include a grained plate conduit groove, a plate surface irregularity, a cloth surface texture, an irregular surface texture, a sand texture, a hair line, and a fine line groove. From the viewpoint of improving the designability, it is preferable that the shape of the concave portion is a shape synchronized with the pattern of the decorative layer. For example, in the case where the pattern layer is in the form of a grain, if the grained plate conduit groove is selected as the shape of the concave portion and the grains of the grain layer and the concave portion of the pattern layer are synchronized with each other, a decorative sheet having a more realistic, Can be obtained.

(Production method of toilet sheet)

Regarding the method for producing a decorative sheet of the present invention, a decorative sheet having a substrate, a decorative layer, an adhesive layer, a resin layer, a primer layer and a surface protective layer in this order, which is one preferred embodiment of the decorative sheet of the present invention, The manufacturing method will be described.

The decorative sheet of the present invention comprises a step (1) of forming a decorative layer on a substrate, a step (2) of forming a resin layer on the decorative layer, and a step of applying a curable resin composition on the resin layer, And a step (3) of forming a protective layer can be sequentially performed.

Step (1) is a step of forming a decorative layer on a substrate. The decorative layer is formed by applying the ink used for forming the decorative layer on the substrate to dispose the desired colored layer and the pattern layer. This ink is applied by a known method such as a gravure printing method, a bar coating method, a roll coating method, a reverse roll coating method and a comma coating method, preferably by a gravure printing method.

 When the substrate is subjected to the surface treatment, when the decorative layer is formed, when the primer layer is formed between the substrate and the decorative layer, it may be disposed before the decorative layer is formed, (Back side) of the opposite side may be disposed after formation of the decorative layer. The primer layer can be formed by applying the resin composition constituting the primer layer by a known method such as a gravure printing method, a bar coating method, a roll coating method, a reverse roll coating method or a comma coating method.

Step (2) is a step of forming a resin layer on the decorative layer. The resin layer may be formed by applying an adhesive to the substrate having the decorative layer as described above to form an adhesive layer, and then using the resin composition constituting the resin layer, the resin layer is subjected to extrusion lamination, dry lamination, wet lamination, Or the like, and then laminated and formed.

When the resin layer is subjected to the surface treatment, the surface treatment may be performed after the resin layer is formed.

When a primer layer is formed between the resin layer and the surface protective layer, a primer layer may be formed using the resin composition constituting the primer layer after the resin layer is formed.

Step (3) is a step of applying a curable resin composition on a resin layer and curing the surface to form a surface protective layer.

The surface protective layer is obtained by applying an ionizing radiation curable resin composition comprising the ionizing radiation curable resin described above onto a resin layer or a primer layer formed on the resin layer as desired, and curing the composition. When a resin layer is not formed, a decorative layer may be formed on a substrate sheet, and then a curable resin composition may be applied and cured to form a surface protective layer.

The application of the resin composition for forming the surface protective layer is preferably carried out in a known manner such as a gravure coat, a bar coat, a roll coat, a reverse roll coat, a comma coat or the like so that the thickness after curing becomes a predetermined thickness Preferably, it is performed by a gravure coat.

When an ionizing radiation-curable resin composition is used to form the surface protective layer, the uncured resin layer formed by applying the resin composition is irradiated with ionizing radiation such as electron beams or ultraviolet rays to form a surface protective layer by making a cured product. When an electron beam is used as the ionizing radiation, the acceleration voltage can be suitably selected according to the resin to be used and the thickness of the layer, but it is preferable to cure the uncured resin layer at an acceleration voltage of usually about 70 to 300 kV .

The irradiation dose is preferably such that the crosslinking density of the ionizing radiation curable resin is saturated, and is usually selected in the range of 5 to 300 kGy (0.5 to 30 Mrad), preferably 10 to 50 kGy (1 to 5 Mrad).

The electron beam source is not particularly limited, and various electron beam accelerators such as a Cocroft Walton type, a Bandegraph type, a resonant transformer type, an insulating core transformer type, a linear type, a dinamitron type and a high frequency type can be used.

When ultraviolet rays are used as the ionizing radiation, those containing ultraviolet rays having a wavelength of 190 to 380 nm are radiated. The ultraviolet ray source is not particularly limited, and for example, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a carbon arc, or the like is used.

In the case of using a thermosetting resin composition for forming the surface protective layer, a heat treatment according to the resin composition to be used may be performed and cured to form a surface protective layer.

In the case of forming the concave portion in the surface protective layer, for example, embossing is preferably employed in consideration of ease of operation. The embossing may be carried out by a conventional method using a known sheet or embossing machine.

When the embossing is carried out, for example, the decorative sheet is preferably heated to a temperature of not less than 80 ° C and not more than 260 ° C, more preferably not less than 85 ° C and not more than 160 ° C, and more preferably not less than 100 ° C and not more than 140 ° C, The span can be pressed and embossed.

[Cosmetics]

The cosmetic material of the present invention comprises an adherend and the above-described cosmetic sheet of the present invention, specifically, a face requiring decoration of the adherend and a face of the face sheet of the face sheet facing each other. That is, the cosmetic material of the present invention has at least the adherend material, the substrate, and the surface protective layer in this order. 3 is a schematic view showing a cross section of an example of a preferred embodiment of the cosmetic material of the present invention. The cosmetic material 20 of the present invention shown in Fig. 3 has the adherend 21, the adhesive layer 22 and the cosmetic sheet 10 of the present invention in this order.

(Adhered material)

As the adherend, plate materials such as flat plates and curved plates of various kinds of materials, three-dimensional shaped articles, sheets (or films), and the like can be given. Woody materials used as plate materials and three-dimensional shaped articles such as wood veneer boards made of various woods such as cedar, cypress, pine, and royal wood, wood plywood, particle board, wood fiber board such as MDF (medium density fiber board) A metal member used as a sheet material such as iron or aluminum, a steel sheet, a three-dimensional article, or a sheet; Ceramics such as ceramics, ceramics and the like, non-cement materials such as gypsum, and non-ceramic materials such as ALC (lightweight foamed concrete), and the like; (Acrylonitrile-butadiene-styrene copolymer) resin, a phenol resin, a vinyl chloride resin, a cellulose resin, and a rubber, a three-dimensional shaped article, Or a resin member used as a sheet or the like. These members may be used singly or in combination of plural kinds.

The material to be adhered may be appropriately selected from those described above according to the purpose of use. In the case where the interior material of a building such as a wall, a ceiling, a floor or the like is used as a window or a manipulation member such as a window frame, door, railings, A wood member, a metal member, and a resin member. In the case of using a window such as an exterior member such as a doorway door, a window frame or a door, it is preferable that the metal member and the resin member are selected At least one kind of member.

The thickness of the adherend may be appropriately selected depending on the application and the material, and is preferably 0.1 mm or more and 10 mm or less, more preferably 0.3 mm or more and 5 mm or less, and still more preferably 0.5 mm or more and 3 mm or less.

(Adhesive layer)

The adherend and the decorative sheet are preferably bonded together through an adhesive layer in order to obtain excellent adhesion. That is, the cosmetic material of the present invention is preferably a member having at least an adhering material, an adhesive layer, a substrate and a surface protective layer in this order.

The adhesive used for the adhesive layer is not particularly limited, and known adhesives can be used. For example, adhesives such as a heat sensitive adhesive and a pressure sensitive adhesive are preferably used. Examples of the resin used for the adhesive constituting the adhesive layer include acrylic resin, polyurethane resin, vinyl chloride resin, vinyl acetate resin, vinyl chloride-vinyl acetate copolymer resin, styrene-acrylic copolymer resin, polyester resin, These may be used singly or in combination of plural kinds. Further, a two-part curing type polyurethane-based adhesive or polyester-based adhesive using an isocyanate compound or the like as a curing agent can also be applied.

A pressure-sensitive adhesive may be used for the adhesive layer. As the pressure-sensitive adhesive, a pressure-sensitive adhesive such as an acrylic type, a urethane type, a silicone type or a rubber type can be suitably selected and used.

The adhesive layer can be formed by applying the above-mentioned resin in a form capable of applying a solution or an emulsion or the like by means of a coating method such as a gravure printing method, a screen printing method or a reverse coating method using a gravure plate and drying.

The thickness of the adhesive layer is not particularly limited, but is preferably 1 占 퐉 or more and 100 占 퐉 or less, more preferably 5 占 퐉 or more and 50 占 퐉 or less, and further preferably 10 占 퐉 or more and 30 占 퐉 or less, from the viewpoint of obtaining excellent adhesiveness .

(Manufacturing method of cosmetic material)

The cosmetic material can be manufactured through a process of laminating a decorative sheet and an adherend.

This step is a step of laminating the adherend and the decorative sheet of the present invention, and the surface of the decorative sheet to be decorated and the surface of the decorative sheet of the decorative sheet are opposed to each other. Examples of the method of laminating the adherend and the decorative sheet include a lamination method in which a decorative sheet is pressed onto a plate-shaped adherend with a pressure roller through an adhesive, and laminated, A lapping process in which a decorative sheet is successively pressed and adhered to a plurality of side faces constituting the adherend by rollers having different orientations, and a lapping process in which the silicone rubber sheet is laminated until a predetermined temperature at which the decorative sheet fixed to the fixing frame is softened A vacuum molding process in which a vacuum molding die is heated on a softened decorative sheet heated by a heater, and at the same time air is sucked from a vacuum forming die through a vacuum pump or the like to adhere the decorative sheet to a vacuum forming die, have.

In the case of using a hot-melt adhesive (heat-sensitive adhesive) in the laminating or lapping process, it is preferable that the heating temperature is 160 ° C or more and 200 ° C or less in the case of the reactive hot- Or more and 130 占 폚 or less. In the case of the vacuum forming process, it is generally carried out while heating, and it is preferably from 80 캜 to 130 캜, more preferably from 90 캜 to 120 캜.

The cosmetic material obtained as described above can be arbitrarily cut and subjected to arbitrary decorations such as grooving and chamfering using a cutting machine such as a router or a cutter on the surface or the forehead. After the decorative sheet is bonded to a steel sheet or the like, bending processing such as V-cut processing or lapping processing may be performed. A cabinet such as a kitchen, a furniture or a pharmacopoeial product, an office automation equipment, or the like other than a window or an operation member of an interior or exterior member of a building such as a wall, a ceiling or a floor, a window frame, a door, a railing, The interior surface of a vehicle, or an exterior member of a vehicle.

Example

Next, the present invention will be described in more detail by way of examples, but the present invention is not limited by these examples.

(Evaluation and measurement method)

(1) Measurement of martens hardness

The Martens hardness of the decorative sheet obtained in each of the Examples and Comparative Examples was measured by the following method.

A pyramidal diamond indenter was continuously applied to the surface of the sample (surface protective layer) at room temperature (23 ° C) while continuously increasing the load, using a micro-hardness tester (micro hardness tester, "Picodenter HM- The test load F (N) at the time when the indentation depth reaches 2 mu m is measured and the surface area A (mm < 2 >) is calculated from the length of the diagonal line of the pyramidal recess formed on the surface, The Martens hardness was calculated by dividing the load F (N) by the surface area A.

(2) Evaluation of processing characteristics (lapping processing)

Regarding the cosmetic material obtained in each of the Examples and Comparative Examples, the state of the corner portion (bent portion) was visually observed and observed, and evaluated according to the following criteria. In addition, when "+" is described along with the following criteria in the table, "+" indicates that "it is more excellent but it does not reach the evaluation in one step". For example, "B ⁺ " indicates that it is superior to "B" but not "A".

A: No change in appearance was observed at the corner portion (bent portion).

B: In the corner portion (bent portion), a slight whitening was confirmed, but no crack was observed.

C: A slight whitening and cracks were observed at the corner portion (bent portion).

D: Significant whitening and cracks were observed at the corner portion (bent portion).

(3) Evaluation of weatherability

With respect to the cosmetic material obtained in each of the examples and the comparative example, the conditions of the 18-minute rainfall during the black panel temperature of 63 DEG C for 120 minutes were measured using a Sunshine weather meter (" WEL-300 ", manufactured by Suga Shikki K.K.) And left to stand for 6000 hours. The appearance of the cosmetic after the weathering test was visually observed and observed and evaluated according to the following criteria.

A: No change in appearance was observed.

B: Very slight color change was confirmed.

C: A slight hue change was confirmed.

D: At least one of a remarkable change in hue, flaking between layers, and cracks was confirmed.

(4) Evaluation of durability

The surface of each of the decorative sheets obtained in each of the examples and the comparative examples was subjected to 10 reciprocating operations at a load of 300 g / m 2 using a steel wool ("BONSTAR # 0000" manufactured by Nippon Steel Wool Co., Ltd.) , And a rubbing test was conducted. The surface condition after the test was visually observed, and the evaluation was made according to the following criteria.

A: No scratches, no change in gloss was observed.

B: Very slight scratches and extremely slight changes in gloss were observed.

C: Change in slight scratches and slight gloss was confirmed.

D: Scratches were confirmed, and remarkable gloss change was confirmed.

(5) Evaluation of designability

The decorative properties of the cosmetic materials obtained in the respective Examples and Comparative Examples were evaluated based on the following criteria.

A: High designability was confirmed by the excellent texture due to the concave portion.

B: sufficient designability was confirmed by the texture of the concave portion.

C: Although the texture due to the concave portion was small, designability was confirmed.

D: There was no texture due to the recess, and the design was low.

Example  One

(White pigment: rutile type titanium oxide (average particle diameter: 0.25 mu m), content: 10 mass%)) on which a double-sided corona discharge treatment was performed (Containing 40% by mass of rutile titanium oxide (average particle diameter: 0.25 占 퐉) as a white pigment) having a two-liquid curing type acrylic-urethane resin as a binder was applied on one side of the substrate by gravure printing, (Thickness: 3 mu m) was formed on the other surface of the substrate, and a two-liquid curing type urethane-super screen mixed resin composition was applied to the other surface to form a back primer layer (thickness: 2 mu m).

A transparent polyurethane resin adhesive was applied on the decorative layer to form an adhesive layer (thickness after drying: 3 mu m), and a transparent polypropylene resin was heated and melt extruded by a T die extruder to obtain a transparent resin layer (thickness: 80 mu m) .

Subsequently, after the surface of the resin layer was subjected to corona discharge treatment, a composition obtained by mixing 100 parts by mass of a resin composition for forming a primer layer described below and 5 parts by mass of hexamethylene diisocyanate (curing agent) was applied by gravure printing to form a primer layer (Thickness after drying: 4 mu m) was formed.

The following ionizing radiation curable resin composition was applied on the primer layer by a roll coating method to form an uncured resin layer and irradiated with electron beams (voltage of 175 KeV, 5 Mrad (50 kGy) The ground layer was cured to obtain a surface protective layer (thickness: 5 mu m). Thereafter, emboss processing was performed from the side of the surface protective layer to form a grain conduit shape having a concave portion with a maximum depth of 50 mu m to obtain a decorative sheet.

An adhesive layer (thickness: 20 mu m) was formed by applying a polyurethane-based thermosensitive adhesive (hot melt adhesive, " PUR704 ", manufactured by Claritit Japan Co.) to the substrate of the obtained decorative sheet. A decorative material (material: vinyl chloride) having an L-shaped cross section was made to follow the decorative sheet, and the decorative material and the decorative sheet were adhered to each other to produce a cosmetic material. The above-mentioned evaluation of the cosmetic sheet and the makeup member was carried out, and the evaluation results are shown in Table 1.

(A resin composition for forming a primer layer)

Binder: Mixture of polycarbonate-based urethane-acrylic copolymer and acrylic polyol resin

Ultraviolet absorber A: 3% by mass of the hydroxyphenyltriazine compound ("TINUVIN 479", BASF) represented by the above general formula (2)

Ultraviolet absorber B: 12% by mass of a hydroxyphenyltriazine compound ("TINUVIN400", BASF) represented by the following general formula (3)

Light stabilizer a: 3 mass% of hindered amine light stabilizer (bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, "TINUVIN 123"

(Ionizing radiation curable resin composition)

Ionizing radiation curable resin A: urethane acrylate oligomer (weight average molecular weight: 4,000, number of functional groups: 3)

Ultraviolet absorber A: 1% by mass of the hydroxyphenyltriazine compound ("TINUVIN 479", BASF) represented by the above general formula (2)

Light stabilizer a: 2 mass% of hindered amine light stabilizer (bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, "TINUVIN 123"

Example  2, 3, and Comparative Example  1, 2

The same procedures as in Example 1 were carried out except that the ionizing radiation curable resin in the ionizing radiation curable resin composition was changed to the following ionizing radiation curable resins B, C, D and E in Example 1, The decorative sheets and cosmetic materials of Examples 1 and 2 were produced. The above-mentioned evaluation of the cosmetic sheet and the makeup member was carried out, and the evaluation results are shown in Table 1.

Ionizing radiation curable resin B: urethane acrylate oligomer (weight average molecular weight: 7,000, number of functional groups: 3)

Ionizing radiation curable resin C: urethane acrylate oligomer (weight average molecular weight: 3,000, number of functional groups: 3)

Ionizing radiation-curable resin D: urethane acrylate oligomer (weight average molecular weight: 2,000, number of functional groups: 3)

Ionizing radiation-curable resin E: urethane acrylate oligomer (weight average molecular weight: 8,000, number of functional groups: 3)

Example  4

In Example 1, the light stabilizer a (hindered amine light stabilizer (bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, "TINUVIN 123" , Manufactured by BASF Co., Ltd.) was contained in an amount of 1 mass%, to prepare a decorative sheet and a cosmetic material. The above-mentioned evaluation of the cosmetic sheet and the makeup member was carried out, and the evaluation results are shown in Table 1.

Example  5

In the printing ink used for forming the decorative layer in Example 1, the above-mentioned light stabilizer a (hindered amine light stabilizer (bis (1-octyloxy-2,2,6,6-tetramethyl- Nyl) sebacate, " TINUVIN 123 ", manufactured by BASF) was contained in an amount of 1% by mass. The above-mentioned evaluation of the cosmetic sheet and the makeup member was carried out, and the evaluation results are shown in Table 1.

Example  6

In the printing ink used for forming the base material and the decorative layer in Example 1, the light stabilizer a (hindered amine light stabilizer (bis (1-octyloxy-2,2,6,6-tetramethyl- (Manufactured by BASF)) was contained in an amount of 1% by mass based on the total amount of the composition of the present invention. The above-mentioned evaluation of the cosmetic sheet and the makeup member was carried out, and the evaluation results are shown in Table 1.

Example  7

The procedure of Example 1 was repeated, except that the resin composition for forming a primer layer was replaced with a resin composition that did not contain the light stabilizer a and emboss processing was performed at a maximum depth of 140 탆 in the recess A toilet seat and a toilet were made. The above-mentioned evaluation of the cosmetic sheet and the makeup member was carried out, and the evaluation results are shown in Table 1.

Example  8

In the same manner as in Example 1 except that the ultraviolet absorber A in the ionizing radiation curable resin composition was replaced with an ultraviolet absorber C (benzotriazole ultraviolet absorber, 2- (5-chloro-benzotriazolyl) -6-tert- Quot; manufactured by BASF Corporation), a decorative sheet and a cosmetic material of Example 8 were produced. The above-mentioned evaluation of the cosmetic sheet and the makeup member was carried out, and the evaluation results are shown in Table 1.

Example  9

A decorative sheet and a cosmetic material were produced in the same manner as in Example 1 except that the embossing process was carried out in the same manner as in Example 1 except that the maximum depth of the concave portion was 10 탆. The above-mentioned evaluation of the cosmetic sheet and the makeup member was carried out, and the evaluation results are shown in Table 1.

The decorative sheet of the present invention was excellent in processing characteristics, and when it was used as a cosmetic material, it was confirmed that fine cracks were not generated in the bent portion, resulting in excellent weather resistance. Further, since the decorative sheet of the present invention is also excellent in durability and designability, it has been confirmed that the decorative sheet using the decorative sheet has excellent weather resistance and designability. In Example 8, the ultraviolet absorber in the ionizing radiation curable resin composition was a benzotriazole ultraviolet absorber. However, the hydroxyphenyltriazine compound used in the other examples, particularly the hydroxyphenyl triazine compound represented by the formula (2) It was confirmed that when triazine compounds were used, excellent weather resistance was obtained.

The maximum depth D of the concave portion was set to 50 μm (the maximum depth D of the concave portion corresponds to the thickness of the decorative sheet T and D = 0.32 × T (D) / (T) = 0.32 ) And the decorative sheets of Examples 7 to 140 占 퐉 ((D) = 0.90 占 (T), (D) / (T) = 0.90) (D) = 0.06 x (T), and (D) / (T) = 0.06) in Example 9, and a superior texture was obtained.

On the other hand, in Comparative Example 1 in which the Martens hardness was as large as 26 N / mm 2, no machining characteristics were obtained, and fine cracks were generated in the bent portion, resulting in poor weather resistance. In Comparative Example 2 in which the Martens hardness was as low as 8 N / mm < 2 >, the machining characteristics were obtained, so that weather resistance was also obtained, but the durability was poor.

In the decorative sheet of Example 1, the content of the ultraviolet absorber in the primer layer was 18.3 parts by mass based on 100 parts by mass of the curable resin constituting the primer layer, and the content of the ultraviolet absorber in the surface protective layer Is added in an amount of 1.0 part by mass based on 100 parts by mass of the curable resin constituting the protective layer. In other words, the content of the ultraviolet absorber in the primer layer is larger than the content of the ultraviolet absorber in the surface protective layer. By such a constitution, the ultraviolet absorber can be prevented from bleeding out, Was obtained. The decorative sheet of another embodiment can also be said in the same manner as the decorative sheet of the first embodiment.

The decorative sheet of the present invention has excellent processing characteristics, weather resistance, and durability, and the cosmetic material using the decorative sheet has excellent weather resistance and durability. As a result, the surface of the cabinets such as kitchens, furniture or pharmacy products, OA appliances, etc., as well as the interior or exterior members of buildings such as walls, ceilings, floors and the like, window frames, doors, railing, windows, It is suitably used for an interior material or an exterior member of a vehicle. Particularly, it is suitably used for a member used in an environment exposed to direct sunlight such as an exterior member such as a doorway door, a window frame of a window sill, a door or the like, taking advantage of its excellent weather resistance and weather resistance.

10: Facial sheet
11: substrate
12: decorative floor
13: Adhesive layer
14: Resin layer
15: Primer layer
16: Surface protective layer
17: backside primer layer
18: White pigment
19: concave portion
20: Toiletries
21: Adhesive
22: Adhesive layer

Claims (21)

At least one of the base material and the surface protective layer comprises a white pigment, the surface protective layer is a cured product of the curable resin composition, and the martens hardness is at least 9 N / mm < 2 ≪ 2 > or less. The decorative sheet according to claim 1, wherein a decorative layer is provided between the substrate and the surface protection layer, and at least one of the base material and the decorative layer comprises a white pigment. A decorative sheet according to claim 2, wherein the substrate and the decorative layer comprise a white pigment. The decorative sheet according to any one of claims 1 to 3, wherein the white pigment is titanium oxide. The decorative sheet according to claim 4, wherein the titanium oxide is rutile titanium oxide. The decorative sheet according to any one of claims 1 to 5, wherein the content of the white pigment in the base material is 1 part by mass or more and 50 parts by mass or less based on 100 parts by mass of the resin constituting the base material. The decorative sheet according to any one of claims 2 to 6, wherein the content of the white pigment in the decorative layer is 5 parts by mass or more and 90 parts by mass or less based on 100 parts by mass of the resin constituting the decorative layer. The optical element according to any one of claims 1 to 7, further comprising at least one layer of a resin layer and a primer layer between the substrate and the surface protective layer, wherein at least one of the surface protective layer and the resin layer and the primer layer Wherein the layer comprises an ultraviolet absorber. The decorative sheet according to claim 8, wherein the content (M ₁ ) of the ultraviolet absorber in at least one of the resin layer and the primer layer is larger than the content (M ₂ ) of the ultraviolet absorber in the surface protective layer. The decorative sheet according to claim 8 or 9, wherein the ultraviolet absorbent contained in at least one of the surface protective layer, the resin layer and the primer layer comprises a triazine-based ultraviolet absorber. The ultraviolet light absorber according to any one of claims 8 to 10, wherein the ultraviolet absorber contained in at least one of the surface protective layer, the resin layer and the primer layer is a hydroxyphenyltriazine compound represented by the following general formula (1) .

(Wherein R ¹¹ is a divalent organic group; R ¹² is an ester group represented by -C (= O) OR ¹⁵ ; and R ¹³ , R ¹⁴ and R ¹⁵ are each independently a monovalent organic group And n ₁₁ and n ₁₂ are each independently an integer of 1 to 5.) The ultraviolet absorber according to claim 11, wherein the ultraviolet absorber is an alkyl ester group in which R ¹¹ is an alkylene group having 1 to 20 carbon atoms, R ¹² and R ¹⁵ are alkyl groups having 1 to 20 carbon atoms, R ¹³ and R ¹⁴ are aryl groups having 6 or more and 20 or less carbon atoms, and n ₁₁ and n ₁₂ are 1, is a hydroxyphenyltriazine compound. The decorative sheet according to any one of claims 1 to 12, wherein the curable resin is an ionizing radiation curable resin. 14. The ionizing radiation curable resin composition according to any one of claims 1 to 13, wherein the curable resin is an ionizing radiation curable resin comprising a urethane (meth) acrylate oligomer having a number of functional groups of 2 or more and 8 or less and a weight average molecular weight of 2,500 to 7,500 Sheets. 15. A decorative sheet according to any one of claims 1 to 14, wherein at least one of the substrate and the surface protective layer comprises a light stabilizer. 16. A decorative sheet according to any one of claims 2 to 15, wherein the decorative layer comprises a light stabilizer. The decorative sheet according to claim 15 or 16, wherein the light stabilizer is a hindered amine light stabilizer. 18. A decorative sheet according to any one of claims 1 to 17, wherein the decorative sheet has a concave portion on a surface of the surface protective layer opposite to the base-side surface. The decorative sheet according to claim 18, wherein the maximum depth D of the concave portion and the thickness T of the decorative sheet have a concave portion having a relationship of 0.15 x T? D? T. 19. A cosmetic material comprising the adherend and the decorative sheet according to any one of claims 1 to 19. 21. A cosmetic material according to claim 20, wherein the adherend comprises at least one member selected from a metal member and a resin member.

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